This invention relates to azeotropic compositions of hydrogen fluoride with halogenated hydrocarbons, their production and their use in manufacturing processes for producing halogenated hydrocarbon mixtures.
Hydrofluorocarbons (HFCs), compounds containing only carbon. hydrogen and fluorine, because of their zero ozone depletion potential, are of interest as environmentally attractive alternatives for chlorofluorocarbons (i.e., CFCs) in such established uses as refrigerants, heat transfer media, foam expansion agents, aerosol propellants, solvents, fire extinguishants and power cycle working fluids, among other applications.
Hydrofluorocarbons can be obtained by reacting chlorohalocarbons with HF using various catalysts. For example CHF2CHF2 (i.e., 1,1,2,2-tetrafluoroethane or HFC-134) can be prepared by reacting 1,1,2,2-tetrachloroethane with HF over a fluorination catalyst/agent in the liquid or vapor phase (see Int. Publ. No. WO 93/25506). Normally, excess HF is used to achieve relatively favorable reactor rates. HF may be removed from the halogenated hydrocarbon components of the product mixture using conventional aqueous solution scrubbing techniques. However, the production of substantial amounts of scrubbing discharge can create aqueous waste disposal concerns.
There remains a need for processes utilizing HF in such product mixtures as well as an interest in developing more efficient processes for the manufacture of hydrofluorocarbons.
This invention provides a process for producing compositions comprising (a) a compound selected from the group consisting of CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2 and (b) at least one saturated compound selected from halogenated hydrocarbons and ethers having the formula:
CnH2n+2-a-bClaFbOc
wherein n is an integer from 1 to 4, a is an integer from 0 to 2n+1, b is an integer from 1 to 2n+2-a, and c is 0 or 1, provided that when c is 1 then n is an integer from 2 to 4, and provided that component (b) does not include the selected component (a) compound, wherein the molar ratio of component (b) to component (a) is between about 1:99 and a molar ratio of HF to component (a) in an azeotrope or azeotrope-like composition of component (a) with HF. This process comprises (A) combining (i) said azeotrope or azeotrope-like composition with (ii) at least one fluorination precursor compound wherein the precursor component (ii) is the fluorination precursor to component (b); and (B) reacting a sufficient amount of the HF from the azeotrope or azeotrope-like composition (i) with precursor component (ii) to provide a composition containing components (a) and (b) in said ratio.
In addition, compositions are provided comprising (a) a compound selected from the group consisting of CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2 (e.g., CHF2CHF2), and (b) at least two saturated compounds selected from halogenated hydrocarbons and ethers having the formula:
CnH2n+2-a-bClaFbOc
wherein n is an integer from 1 to 4, a is an integer from 0 to 2n+1, b is an integer from 1 to 2n+2-a, and c is 0 or 1, provided that when c is 1 then n is an integer from 2 to 4, provided that component (b) does not include the selected component (a) compound, and provided that c is 1 for at least one of the component (b) compounds, wherein the molar ratio of component (b) to component (a) is between about 1:99 and a molar ratio of HF to component (a) in an azeotrope or azeotrope-like composition of component (a) with HF.
The present invention further provides a process for recovering HF from a product mixture comprising HF and CHF2CHF2. The process comprises (1) distilling the product mixture to remove all products which have a lower boiling point than the lowest boiling azeotrope containing HF and CHF2CHF2; and (2) distilling said azeotrope to recover HF as an azeotropic composition containing HF and CHF2CHF2.
Also provided are compositions which consist essentially of hydrogen fluoride in combination with an effective amount of CHF2CHF2 to form an azeotrope or azeotrope-like composition with hydrogen fluoride, said composition containing from about 70.5 to 75.5 mole percent CHF2CHF2.
The present invention provides compositions which consist essentially of hydrogen fluoride and an effective amount of CHF2CHF2 to form an azeotropic combination with hydrogen fluoride. By effective amount is meant an amount which, when combined with HF, results in the formation of an azeotrope or azeotrope-like mixture. As recognized in the art, an azeotrope or an azeotrope-like composition is an admixture of two or more different components which, when in liquid form under given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the individual components, and which will provide a vapor composition essentially identical to the liquid composition undergoing boiling.
An azeotrope is a liquid mixture that exhibits a maximum or minimum boiling point relative to the boiling points of surrounding mixture compositions. An azeotrope is homogeneous if only one liquid phase is present. An azeotrope is heterogeneous if more than one liquid phase is present. Regardless, a characteristic of minimum boiling azeotropes is that the bulk liquid composition is then identical to the vapor composition in equilibrium therewith, and distillation is ineffective as a separation technique. For the purpose of this discussion, azeotrope-like composition means a composition which behaves like an azeotrope (i.e., has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Thus, the composition of the vapor formed during boiling or evaporation of such compositions is the same as or substantially the same as the original liquid composition. Hence, during boiling or evaporation, the liquid composition, if it changes at all, changes only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
Accordingly, the essential features of an azeotrope or an azeotrope-like composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the boiling liquid composition (i.e., no fractionation of the components of the liquid composition takes place). It is also recognized in the art that both the boiling point and the weight percentages of each component of the azeotropic composition may change when the azeotrope or azeotrope-like liquid composition is subjected to boiling at different pressures. Thus an azeotrope or an azeotrope-like composition may be defined in terms of the unique relationship that exists among components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure. It is also recognized in the art that various azeotropic compositions (including their boiling points at particular pressures) may be calculated (see, e.g., W. Schotte, Ind. Eng. Chem. Process Des. Dev. 1980, 19, pp 432-439). Experimental identification of azeotropic compositions involving the same components may be used to confirm the accuracy of such calculations and/or to modify the calculations for azeotropic compositions at the same or other temperatures and pressures.
A composition may be formed which consists essentially of azeotropic combinations of hydrogen fluoride and CHF2CHF2. This includes a composition consisting essentially of from about 24.5 to about 29.5 mole percent HF and from about 75.5 to about 70.5 mole percent CHF2CHF2 (which forms an azeotrope boiling at a temperature from between about xe2x88x9240xc2x0 C. and about 0xc2x0 C. and a pressure from between about 39 kPa and about 240 kPa).
At atmospheric pressure, the boiling points of hydrofluoric acid and HFC-134 are about 19.5xc2x0 C. and xe2x88x9223xc2x0 C., respectively. However, the relative volatility at 105 kPa (15.2 psia) and xe2x88x9220xc2x0 C. of HF and HFC-134 was found to be nearly 1.0 as 25 mole percent HF and 75 mole percent HFC-134 was approached. These data indicate that the use of conventional distillation procedures will not result in the separation of a substantially pure compound because of the low value of relative volatility of the compounds.
To determine the relative volatility of HF with HFC-134, the so-called PTx Method was used. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for various known binary compositions. Use of the PTx Method is described in greater detail in xe2x80x9cPhase Equilibrium in Process Designxe2x80x9d, Wiley-Interscience Publisher, 1970, written by Harold R. Null, on pages 124 to 126, the entire disclosure of which is hereby incorporated by reference. Samples of the vapor and liquid, or vapor and each of the two liquid phases under those conditions where two liquid phases exist, were obtained and analyzed to verify their respective compositions.
These measurements can be reduced to equilibrium vapor and liquid compositions in the cell by an activity coefficient equation model, such as the Non-Random, Two-Liquid (NRTL) equation, to represent liquid phase non-idealities. Use of an activity coefficient equation, such as the NRTL equation, is described in greater detail in xe2x80x9cThe Properties of Gases and Liquidsxe2x80x9d, 4th Edition, publisher McGraw Hill, written by Reid, Prausnitz and Poling, on pages 241 to 387; and in xe2x80x9cPhase Equilibria in Chemical Engineeringxe2x80x9d, published by Butterworth Publishers, 1985, written by Stanley M. Walas, pages 165 to 244; the entire disclosure of each of the previously identified references are hereby incorporated by reference.
Without wishing to be bound by any theory or explanation, it is believed that the NRTL equation can sufficiently predict whether or not mixtures of HF and HFC-134 behave in an ideal manner, and can sufficiently predict the relative volatilities of the components in such mixtures. Thus, while HF has a good relative volatility compared to HFC-134 at low HFC-134 concentrations, the relative volatility becomes nearly 1.0 as 75 mole percent HFC-134 was approached at xe2x88x9220xc2x0 C. This would make it impossible to separate HFC-134 from HF by conventional distillation from such a mixture. Where the relative volatility approaches 1.0 defines the system as forming a near-azeotrope. Where the relative volatility is 1.0 defines the system as forming an azeotrope.
Azeotropes of HF and HFC-134 are formed at a variety of temperatures and pressures. At a pressure of 15.2 psia (105 kPa) and xe2x88x9220xc2x0 C., the azeotrope vapor composition was found to be about 25 mole percent HF and about 75 mole percent HFC-134. Based upon the above finding, it has been calculated that an azeotropic composition of about 29.5 mole percent HF and about 70.5 mole percent HFC-134 can be formed at xe2x88x9240xc2x0 C. and 5.6 psia (39 kPa) and an azeotropic composition of about 24.5 mole percent HF and about 75.5 mole percent HFC-134 can be formed at 0xc2x0 C. and 34.8 psia (240 kPa). Accordingly, the present invention provides an azeotrope or azeotrope-like composition consisting essentially of from about 29.5 to 24.5 mole percent HF and from about 70.5 to 75.5 mole percent HFC-134, said composition having a boiling point from about xe2x88x9240xc2x0 C. at 39 kPa to about 0xc2x0 C. at 240 kPa.
The HFC-134 can be separated from its azeotrope with HF by conventional means such as neutralization and decantation. However the azeotropic composition of HFC-134 and HF is useful as recycle to a fluorination reactor, where the recycled HF can function as a reactant and the recycled HFC-134 can function to moderate the heat of reaction. It will also be apparent to one of ordinary skill in the art that distillation including azeotropes with HF can typically be run under more convenient conditions than distillation without HF (e.g., where HF is removed prior to distillation).
The HFC-134/HF azeotrope, as well as HFC-134a/HF, HFC-134a/HF, HFC-125/HF, HFC-152a/HF, HFC-245ca/HF and HFC-338pcc/HF azeotropes can be used as an HF source to fluorinate numerous compounds. Optionally, such fluorinations can employ a fluorination catalyst. The fluorinations can be done in the liquid phase using typical catalysts such as SbCl5. The fluorinations can also be done in the vapor phase using typical catalysts such as Cr2O3. Of note, however, are vapor phase fluorinations in the presence of a catalytic composition comprising cubic chromium trifluoride (i.e., chromium trifluoride having an X-ray diffraction powder pattern as shown in Table I.
Cubic chromium trifluoride may be prepared from CrF3xe2x80xa2XH2O, where X is 3 to 9, preferably 4, by heating in air or an inert atmosphere (e.g., nitrogen or argon) at 350xc2x0 C. to 400xc2x0 C. for 3 to 12 hours, preferably 3 to 6 hours. The color of cubic chromium trifluoride is dark green. Cubic chromium trifluoride is useful by itself and together with other chromium compounds, as a catalytic material. Of note are catalyst compositions comprising chromium wherein at least 10% of the chromium is in the form of cubic chromium trifluoride, particularly catalyst compositions wherein at least 25% of the chromium is in the form of cubic chromium trifluoride, and especially catalyst compositions wherein at least 60% of the chromium is in the form of cubic chromium trifluoride. The chromium, including the cubic chromium trifluoride can be supported on and/or physically mixed with materials such as carbon, aluminum fluoride, fluorided alumina, lanthanum fluoride, magnesium fluoride, calcium fluoride, zinc fluoride and the like. Preferred are combinations including cubic chromium trifluoride in combination with magnesium fluoride and/or zinc fluoride. Chromium trifluoride catalyst which consists essentially of cubic chromium trifluoride can also be prepared and used in accordance with this invention.
By fluorination precursors to the component (b) compound(s) is meant compounds which react with HF (optionally in the presence of a fluorination catalyst) to produce the corresponding component (b) compound(s). Fluorination precursors include saturated compounds having the formula
CnH2n+2-a-bCla+xFb-xOc
wherein x is an integer from 1 to b. Examples of saturated precursors and corresponding products are as follows:
Fluorination precursors also include unsaturated compounds having the formula
CnH2n+1-a-bCla+yFb-y-1Oc
wherein y is an integer from 0 to b-1. Examples of unsaturated precursors and corresponding products are as follows:
Of particular note are processes where for component (b) a is 0 and b is 2n+1, or less.
The precursor compounds, either individually or in mixed blends, can be fluorinated with the HF azeotrope to provide a variety of compositions wherein the ratio of the fluorination product(s) to a compound selected from the group consisting of CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2 is about 1:99, or more (depending upon the azeotropic combination of said compound and HF used, the particular precursor(s) and the degree of fluorination). These fluorinations include processes for producing compositions wherein the molar ratio of component (b) to said compound (a) is between about 1:99 and 15:85 when compound (a) is CHF2CF3; is between about 1:99 and about 29.5:70.5 when compound (a) is CHF2CHF2; is between about 1:99 and about 27:73 when compound (a) is CH2FCF3; is between about 1:99 and about 13.8:86.2 when compound (a) is CH3CF3; is between about 1:99 and about 8.5:91.5 when compound (a) is CH3CHF2; is between about 1:99 and about 83:17 when compound (a) is CH2FCF2CHF2; and is between about 1:99 and about 96.5:3.5 when compound (a) is CHF2CF2CF2CHF2. This process comprises (A) combining (i) an azeotrope or azeotrope-like composition consisting essentially of compound (a) and HF wherein the ratio of HF to compound (a) is at least equal to the desired ratio of component (b) to the respective component (a) compound, with the precursor component (ii).
Of note are embodiments of this fluorination where the HF azeotropes of a compound selected from the group consisting of CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2 which are combined with the precursor(s) are obtained by (1) distilling a product mixture comprising HF and said compound (a) to remove all products which have a lower boiling point than the lowest boiling azeotrope containing HF and said compound (a); and (2) distilling said azeotrope to recover HF as an azeotropic composition containing HF and said compound (a). Of note are processes where the fluorination precursors include precursors for at least two saturated compounds of the formula CnH2n+2-a-bClaFbOc where c is 1 for at least one of said saturated compounds.
These embodiments thus involve azeotropic distillation of HF with a compound selected from the group consisting of CHF2CF3 (i.e., 1,1,1,2,2-pentafluoroethane or HFC-125); CHF2CHF2 (i.e., 1,1,2,2-tetafluoroethane or HFC-134); CH2FCF3 (i.e., 1,1,1,2-tetrafluoroethane or HFC-134a); CH3CF3 (i.e., 1,1,1-trifluoroethane or HFC-143a); CH3CHF2 (i.e., 1,1,1-difluoroethane or HFC-152a); CH2FCF2CHF2 (i.e., 1,1,2,2,3-pentafluoropropane or HFC-245ca); and CHF2CF2CF2CHF2 (i.e., 1,1,2,2,3,3,4,4-octafluorobutane or HFC-338pcc). The product mixtures distilled can be obtained from a variety of sources. These sources include product mixtures produced by fluorination with HF of CHCl2FCF3 to afford HFC-125/HF; fluorination with HF of CHCl2CHCl2 to afford HFC-134/HF; fluorination with HF of CH2ClCF3 to afford HFC-134a/HF; fluorination with HF of CH3CCl3 to afford HFC-143a/HF; fluorination with HF of CH2xe2x95x90CHCl to afford HFC-152a/HF; and fluorination with HF of CH2ClCF2CHF2 to afford HFC-245ca/HF. The described catalytic fluorination with HF reactions can be done in either the liquid or vapor phase using procedures known in the art.
The product mixture may be distilled to remove all products which have a lower boiling point than the lowest boiling azeotrope containing HF and a compound selected from the group consisting of CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2. Such low-boiling materials can include, for example, HCl. For continuous processes, distillate and azeotropes with higher boiling points can be advantageously removed from appropriate sections of the distillation column.
The lowest boiling azeotrope containing HF and one of the following compounds, CHF2CF3, CHF2CHF2, CH2FCF3, CH3CF3, CH3CHF2, CH2FCF2CHF2 and CHF2CF2CF2CHF2 may then be distilled such that HF is recovered as an azeotropic composition containing HF together with one of the said compounds.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CHF2CF3) consists essentially of HF and CHF2CF3, HF may be recovered as an azeotrope consisting essentially of CHF2CF3 and HF. If excess amounts of CHF2CF3 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CHF2CF3 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9250xc2x0 C. and about 50xc2x0 C. and the pressure is between 92 kPa and 2674 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 85 to about 89 mole percent CHF2CF3 are recovered. HF may be recovered for example, from a product mixture including CHF2CF3 formed by the reaction of CHCl2CF3 with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CHF2CHF2) consists essentially of HF and CHF2CHF2, HF may be recovered as an azeotrope consisting essentially of CHF2CHF2 and HF. If excess amounts of CHF2CHF2 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CHF2CHF2 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9240xc2x0 C. and about 0xc2x0 C. (e.g., about xe2x88x9220xc2x0 C.) and the pressure is between 39 kPa and 240 kPa (e.g., about 105 kPa). Examples of temperatures and pressures suitable for azeotropic formation are provided below. The process of this invention includes embodiments where azeotropic compositions containing from about 70.5 to about 75.5 mole percent CHF2CHF2 are recovered. HF may be recovered for example, from a product mixture including CHF2CHF2 formed by the reaction of CHCl2CHCl2 with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CH2FCF3) consists essentially of HF and CH2FCF3, HF may be recovered as an azeotrope consisting essentially of CH2FCF3 and HF. If excess amounts of CH2FCF3 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CH2FCF3 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9242xc2x0 C. and about 56xc2x0 C. and the pressure is between 50 kPa and 1600 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 73 to about 87 mole percent CH2FCF3 are recovered. HF may be recovered for example, from a product mixture including CH2FCF3 formed by the reaction of CH2ClCF3 with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CH3CF3) consists essentially of HF and CH3CF3, HF may be recovered as an azeotrope consisting essentially of CH3CF3 and HF. If excess amounts of CH3CF3 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CH3CF3 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9225xc2x0 C. and about 70xc2x0 C. and the pressure is between 267 kPa and 4101 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 86.2 to about 95 mole percent CH3CF3 are recovered. HF may be recovered for example, from a product mixture including CH3CF3 formed by the reaction of CCl3CF3 with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CH3CHF2) consists essentially of HF and CH3CHF2, HF may be recovered as an azeotrope consisting essentially of CH3CHF2 and HF. If excess amounts of CH3CHF2 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CH3CHF2 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about 45xc2x0 C. and about 95xc2x0 C. and the pressure is between 1034 kPa and 3198 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 91.5 to about 99 mole percent CH3CHF2 are recovered. HF may be recovered for example, from a product mixture including CH3CHF2 formed by the reaction of CH2xe2x95x90CHCl with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CH2FCF2CHF2) consists essentially of HF and CH2FCF2CHF2, HF may be recovered as an azeotrope consisting essentially of CH2FCF2CHF2 and HF. If excess amounts of CH2FCF2CHF2 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CH2FCF2CHF2 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9210xc2x0 C. and about 130xc2x0 C. and the pressure is between 43 kPa and 3385 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 17 to about 48 mole percent CH2FCF2CHF2 are recovered. HF may be recovered for example, from a product mixture including CH2FCF2CHF2 formed by the reaction of CH2ClCF2CHF2 with HF.
Where the mixture (after distilling components boiling at lower temperatures than the lowest boiling azeotrope of HF with CHF2CF2CF2CHF2) consists essentially of HF and CHF2CF2CF2CHF2, HF may be recovered as an azeotrope consisting essentially of CHF2CF2CF2CHF2 and HF. If excess amounts of CHF2CF2CF2CHF2 or HF remain after azeotropes are recovered from these mixtures, such excess may be recovered as a relatively pure compound. The distillation of azeotropes containing HF and CHF2CF2CF2CHF2 may be done at a wide variety of temperatures and pressures. Typically the temperature is between about xe2x88x9240xc2x0 C. and about 145xc2x0 C. and the pressure is between 7.3 kPa and 4115 kPa. The process of this invention includes embodiments where azeotropic compositions containing from about 3.5 to about 36.8 mole percent CHF2CF2CF2CHF2 are recovered. HF may be recovered for example, from a product mixture including CHF2CF2CF2CHF2 formed by the fluorination of CCl3CF2CF2CCl3 to CClF2CF2CF2CClF2 followed by hydrogenolysis in the presence of HF and HCl from the fluorination.
The fluorination product components containing component (a) and component (b) may be separated by conventional means such as distillation, selective sorption and/or decantation. The compositions of this invention comprising components (a) and (b) (including at least one ether) are useful, for example, as aerosol propellants, fire extinguishants and/or refrigerants.
Some of the compounds of the component (a)/component (b) combinations may form HCl azeotropes. The HCl can be separated from those combinations by extractive distillation or sorption on activated carbon. A number of the combinations may boil too close together to separate by distillation forming zeotropic blends (i.e., blends boiling within a limited temperature range). Some of the combinations may form binary or even ternary azeotropes. The azeotropes, zeotropes and individual compounds can be collected form different parts of a distillation column.
The distillation equipment and its associated feed lines, effluent lines and associated units should be constructed of materials resistant to hydrogen fluoride, hydrogen chloride and chlorine. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, and the well-known high nickel alloys, such as Monel(copyright) nickel-copper alloys, Hastelloy(copyright) nickel-based alloys and, Inconel(copyright) nickel-chromium alloys. Also suitable for reactor fabrication are such polymeric plastics as polytrifluorochloroethylene and polytetrafluoroethylene, generally used as linings.
Of note are compositions comprising (a) CHF2CHF2 and component (b) wherein the molar ratio of component (b) to CHF2CHF2 is between about 1:99 and about 29.5:70.5. Also of note are processes for producing compositions comprising (a) CH2FCF3 and (b) CH3CF3, particularly processes where an azeotrope of CH2FCF3 and HF is combined with CH2xe2x95x90CF2.